CN102361908B - Process for preparing unsaturated polyester - Google Patents
Process for preparing unsaturated polyester Download PDFInfo
- Publication number
- CN102361908B CN102361908B CN201080013579.5A CN201080013579A CN102361908B CN 102361908 B CN102361908 B CN 102361908B CN 201080013579 A CN201080013579 A CN 201080013579A CN 102361908 B CN102361908 B CN 102361908B
- Authority
- CN
- China
- Prior art keywords
- benzoquinones
- resin
- alkyl
- unsaturated polyester
- replaces
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 229920006305 unsaturated polyester Polymers 0.000 title description 34
- 238000000034 method Methods 0.000 claims abstract description 45
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 40
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 27
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 77
- 239000011347 resin Substances 0.000 claims description 77
- 150000004054 benzoquinones Chemical class 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 239000003085 diluting agent Substances 0.000 claims description 25
- 150000002148 esters Chemical group 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 16
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000003973 paint Substances 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 5
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 7
- 150000002009 diols Chemical class 0.000 abstract description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract 2
- 150000004057 1,4-benzoquinones Chemical class 0.000 abstract 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 38
- 239000003112 inhibitor Substances 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 14
- 239000000178 monomer Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical group 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 2
- SGWZVZZVXOJRAQ-UHFFFAOYSA-N 2,6-Dimethyl-1,4-benzenediol Chemical group CC1=CC(O)=CC(C)=C1O SGWZVZZVXOJRAQ-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- QIXDHVDGPXBRRD-UHFFFAOYSA-N 2,3,5-trimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C(C)=C(C)C1=O QIXDHVDGPXBRRD-UHFFFAOYSA-N 0.000 description 1
- AIACLXROWHONEE-UHFFFAOYSA-N 2,3-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=C(C)C(=O)C=CC1=O AIACLXROWHONEE-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- NPGZGVPKRJYKCI-UHFFFAOYSA-N 2-tert-butyl-6-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=C(C(C)(C)C)C1=O NPGZGVPKRJYKCI-UHFFFAOYSA-N 0.000 description 1
- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical class CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HBPTUDIZKSGJNN-UHFFFAOYSA-N benzoic acid;cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1.OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 HBPTUDIZKSGJNN-UHFFFAOYSA-N 0.000 description 1
- -1 bis--tertiary butyl-2,2 '-methylene Chemical group 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QAEKNCDIHIGLFI-UHFFFAOYSA-L cobalt(2+);2-ethylhexanoate Chemical compound [Co+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QAEKNCDIHIGLFI-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- WAMKWBHYPYBEJY-UHFFFAOYSA-N duroquinone Chemical compound CC1=C(C)C(=O)C(C)=C(C)C1=O WAMKWBHYPYBEJY-UHFFFAOYSA-N 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- PCGJKONMMAOCQK-UHFFFAOYSA-N styrene Chemical compound C=Cc1ccccc1.C=Cc1ccccc1.C=Cc1ccccc1.C=Cc1ccccc1.C=Cc1ccccc1.C=Cc1ccccc1 PCGJKONMMAOCQK-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
The present invention relates to a process for preparing unsaturated polyester resin comprising itaconate ester units as reactive unsaturations, wherein the process comprises reacting at least itaconic acid and/or itaconic anhydride and at least one diol in the presence of benzoquinone and/or alkyl substituted benzoquinone, whereby the total amount of benzoquinone and alkyl substituted benzoquinone is at least 200 ppm.
Description
The present invention relates to a kind of method of preparing unsaturated polyester resin, described unsaturated polyester resin is applicable to manufacturing structure parts, and it comprises itaconic ester unit as the reactive unsaturated group in resin.
At present conventionally comprise large weight phenylethylene as reactive diluent that can copolymerization for obtaining unsaturated polyester resin compositions that structure unit uses.Exist cinnamic result to be, at preparation and setting up period, even during the life-time service in its expection, vinylbenzene may be overflowed, thereby produces less desirable smell, even may produce toxic effect.Therefore expect to reduce cinnamic volatilization.Due to unsaturated polyester resin just can copolymerization this fact, cannot make further reduce and the mechanical property of cured composite material do not produced to adverse influence containing cinnamic amount in cinnamic resin.Therefore need can homopolymerization unsaturated polyester resin.While use in this article, if at least the unsaturated dicarboxylic acid structural unit of 25wt.% be can homopolymerization (that is: be methylene-succinic acid structural unit), can homopolymerization just comprise that itaconic ester unit is regarded as the unsaturated polyester resin of reactive unsaturated group.
But find: unsaturated polyester resin that can homopolymerization is easy to gel (that is: be easy to polymerization) during its preparation, and particularly, when use standard UP building-up process, all raw materials that wherein resin is used mix also condensation at higher temperature.
Concerning the unsaturated polyester for the manufacture of structure unit, with the necessary energy of this unsaturated polyester radical polymerization (that is: solidifying) after reactive diluent dilution.This needs to be avoided gel during being illustrated in the preparation of unsaturated polyester resin.
WO-A-9727253 has described the synthetic of methylene-succinic acid based powders coating resin.In this announcement, do not use standard UP building-up process (all raw materials mixed and condensation at higher temperature that wherein resin is used).By use prepolymer method (wherein the polymkeric substance of hydroxyl-functional or oligopolymer in second step with methylene-succinic acid modification and be condensed to low acid number) or by use acid anhydrides method (wherein making the polymer modification of hydroxyl-functional with the resin of generation high acid value with itaconic anhydride) prepare can homopolymerization methylene-succinic acid base unsaturated polyester.
FR-A-1295841 discloses and has contained the preparation of itaconic ester as the unsaturated polyester of reactive unsaturated group: by use standard unsaturated polyester building-up process under the existence of quinhydrones.Using a shortcoming of quinhydrones is the solidification rate that possible affect resin.Well-known inhibitor may impact the curing characteristics of resin.Therefore, expecting to obtain can be for the preparation of other alternative inhibitor of resin.In addition, in synthesizing, inhibitor used may be to the mechanical property generation adverse influence of cured resin for resin.Consider these, also expecting to obtain can be for the preparation of other alternative inhibitor of resin.Therefore, expecting very much to obtain can be for the preparation of other alternative inhibitor of unsaturated polyester with itaconic ester unit.
The object of this invention is to provide a kind of alternative inhibitor that can be used in standard unsaturated polyester building-up process, for the preparation of comprising the unsaturated polyester of itaconic ester unit as reactive unsaturated group, wherein the viscosity of prepared resin is similar or even lower, and the mechanical property of cured resin is similar or even better.
This object realizes comprising in following method surprisingly: at least make to react under the existence of the benzoquinones that methylene-succinic acid and/or itaconic anhydride and at least one glycol replace at benzoquinones and/or alkyl, the total amount of the benzoquinones that wherein benzoquinones and alkyl replace is 200ppm (with respect to the total amount of preparing unsaturated polyester raw material used) at least.
This is surprising, because the benzoquinones that uses the benzoquinones of 100ppm or alkyl to replace causes resin gel, and does not occur gelation while using the quinhydrones of 100ppm.
The mechanical property of the cured article that extra advantage of the inventive method is the resin based on preparing by the inventive method can improve, particularly HDT.
Preferably, method of the present invention comprises:
(i) by methylene-succinic acid and/or itaconic anhydride and optionally other diprotic acid, at least one glycol and inhibitor add reactor;
(ii) make reactor be heated to 180-200 DEG C temperature until acid number lower than 60;
(iii) by cooling formed resin, be preferably cooled to 20-120 DEG C; And
(iv) dilute described resin with reactive diluent alternatively;
(v) wherein said inhibitor is the benzoquinones that benzoquinones and/or alkyl replace, and the total amount of the benzoquinones that wherein benzoquinones and alkyl replace is 200ppm at least.While use in this article, at least represent greater than or equal to.
Preferably, the total amount of the benzoquinones inhibitor that benzoquinones and alkyl replace is 300ppm at least, and more preferably, the amount of the benzoquinones inhibitor of benzoquinones and alkyl replacement is 400ppm at least.The method can be carried out under the existence of additional inhibitor.Preferably, method of the present invention is at 2000ppm at the most, more preferably carry out under the existence of 750ppm inhibitor at the most.
One preferred embodiment in, present method is to carry out under the existence of benzoquinones replacing at alkyl, may cause like this: compared with using benzoquinones, the viscosity of prepared resin is lower.
Another preferred embodiment in, under the existence of the benzoquinones that present method replaces at benzoquinones and alkyl, carry out.This preferred embodiment in, preferably, under the existence of the benzoquinones that present method replaces at 200ppm alkyl at least and at least under the existence of 200ppm benzoquinones, carry out.Find: use the viscosity aspect that is combined in the prepared resin of reduction of the benzoquinones of benzoquinones and alkyl replacement to there is synergistic effect, kept the thermostability of cured resin simultaneously.
The non-limitative example of the benzoquinones that alkyl replaces is 2-methylbenzoquinone, 2，3-dimethylbenzoquinone, 2,5-phlorone, 2,6-phlorone, trimethylbenzoquinone, tetramethyl-benzoquinone, 2-tertiary butyl benzoquinones, the 2-tertiary butyl-6-methylbenzoquinone.The benzoquinones that preferred alkyl replaces is 2-methylbenzoquinone.
Unsaturated polyester of the present invention comprises the itaconic ester unit with following structural formula as structural unit (building block).
Itaconic ester unit (also referred to as methylene-succinic acid structural unit) contain can with the ethylenic unsaturated group of monomer (unsaturated polyester is diluted therein) copolymerization that can copolymerization.Unsaturated polyester of the present invention can and be prepared as the methylene-succinic acid of unsaturated dicarboxylic acid or the polycondensation of itaconic anhydride by least one glycol.Polycondensation can also for example, and/or be carried out under the existence of other di-carboxylic acid (toxilic acid or maleic anhydride and fumaric acid) containing reactive unsaturated group for example, under the existence of saturated aliphatic dicarboxylic acid or acid anhydrides (oxalic acid, succinic acid, hexanodioic acid, sebacic acid) and/or for example, under the existence of saturated aromatic dicarboxylate or acid anhydrides (phthalic acid or Tetra hydro Phthalic anhydride and m-phthalic acid).In polymerization, can also use other glycol, such as the bisphenol-A of 1,2-PD, ethylene glycol, Diethylene Glycol, triethylene glycol, 1,3-PD, dipropylene glycol, tripropylene glycol, neopentyl glycol, A Hydrogenated Bisphenol A-A or ethoxylated/propoxylated.
According to one preferred embodiment, in unsaturated polyester resin, the molecular weight of glycol is in the scope of 60-250Dalton.One preferred embodiment in, at least partly glycol is selected from Isosorbide or 1,3-PD or the two all has, preferably for example, from non-fossil origin (corn).
Preferably, the total amount of diacid is in the scope of 20 to 80 % by mole, and the total amount of glycol is in the scope of 20 to 80 % by mole, and wherein glycol and diacid add up to 100 % by mole.
Preferably, unsaturated polyester of the present invention can homopolymerization.In unsaturated polyester resin of the present invention, preferably at least the di-carboxylic acid structural unit of 25wt.% is methylene-succinic acid structural unit.More preferably, in unsaturated polyester resin of the present invention, at least the di-carboxylic acid structural unit of 55wt.% is methylene-succinic acid structural unit.
Preferably, unsaturated polyester of the present invention can homopolymerization.Preferably at least 25wt.%, more preferably at least the unsaturated dicarboxylic acid structural unit of 55wt.% is methylene-succinic acid structural unit.
One preferred embodiment in, at least partly methylene-succinic acid or itaconic anhydride for example, from non-fossil origin, corn.
Preferably, contain itaconic ester unit as the unsaturated polyester of reactive unsaturated group by forming as follows: the unsaturated diacid monomer of the methylene-succinic acid monomer of the diol monomer of 33-66 % by mole, 10-66 % by mole, 0-65 % by mole is (except methylene-succinic acid monomer, for example fumaric acid monomer and maleic acid monomer) and the diacid except unsaturated diacid monomer of 0-65 % by mole, the preferably diacid except unsaturated diacid monomer of 0-50 % by mole.
Preferably, the acid number of the unsaturated polyester resin that contains itaconic ester is in the scope of 30-100mg KOH/ (g resin), more preferably in the scope of 35-75mg KOH/ (g resin).While use in this article, according to the acid number of ISO 2114-2000 titration measuring resin.
In one embodiment, in unsaturated polyester resin of the present invention the mol ratio of terminal hydroxy group and carboxylic end group in the scope of 0.33-0.9.In another embodiment, in unsaturated polyester of the present invention the mol ratio of terminal hydroxy group and carboxylic end group in the scope of 1.1-3.
The hydroxyl value of the unsaturated polyester resin that preferably, contains itaconic ester is higher than 25, more preferably in the scope higher than 40mg/g resin.While use in this article, measure the hydroxyl value of the polyester that contains itaconic ester according to ISO 4629-1996.
Preferably, comprising itaconic ester is 300Dalton at least as the molecular weight of the unsaturated polyester of reactive unsaturated group, is preferably at least 500Dalton, is more preferably 750Dalton at least.Preferably, comprising itaconic ester is 10000Dalton at the most as the molecular weight Mn of the unsaturated polyester of reactive unsaturated group, is more preferably 5000Dalton at the most.Determining molecular weight (Mn) as follows: according to ISO 13885-1, in tetrahydrofuran (THF), use polystyrene standards and be the designed suitable post of molecular weight determination by GPC.
In one of the present invention preferred embodiment, molecular weight Mn is in the scope of 750-5000Dalton.
Preferably, the glass transition temperature Tg of unsaturated polyester is at least-70 DEG C and 100 DEG C at the most.If unsaturated polyester is used for building object, preferably, the second-order transition temperature of the unsaturated polyester resin existing in resin combination of the present invention is at least-70 DEG C, is more preferably at least-50 DEG C, is even more preferably at least-30 DEG C.Preferably, the second-order transition temperature of the unsaturated polyester resin existing in resin combination of the present invention is 70 DEG C at the most, is more preferably 50 DEG C at the most, is even more preferably 30 DEG C at the most.While use in this article, Tg measures by DSC method (rate of heating is 5 DEG C/min).
The invention still further relates to a kind of unsaturated polyester resin compositions, it comprises: the benzoquinones that unsaturated polyester resin, benzoquinones and/or the alkyl that contains itaconic ester unit replaces.One preferred embodiment in, this resin combination comprises: the benzoquinones that the unsaturated polyester that contains itaconic ester unit and alkyl replace.In an even preferred embodiment, this resin combination comprises: the benzoquinones that unsaturated polyester, benzoquinones and the alkyl that contains itaconic ester unit replaces.Preferably, the benzoquinones that alkyl replaces is 2-methylbenzoquinone.Preferably, this resin combination comprises the benzoquinones that benzoquinones and alkyl replace, and the total amount of the benzoquinones that wherein benzoquinones and alkyl replace is 200ppm at least, is more preferably 300ppm (with respect to the total amount of resin combination) at least.The total amount of the benzoquinones that conventionally benzoquinones and alkyl replace is 2000ppm at the most, is more preferably 750ppm at the most.Preferably, said composition comprises reactive diluent.
In one embodiment, unsaturated polyester resin of the present invention can be used as powder coating resin.Misev exists " Powder Coatings, Chemistry and Technology " (pp.224-300; 1991, John Wiley) in the preparation method of powder paint compositions has been described, it is incorporated herein by reference.Therefore, the invention still further relates to the powder paint compositions that comprises unsaturated polyester of preparing by method of the present invention.If unsaturated polyester of the present invention is used to powder paint compositions, preferably, the glass transition temperature Tg of unsaturated polyester resin is at least 20 DEG C, more preferably be at least 25 DEG C, even more preferably be at least 30 DEG C and 100 DEG C at the most, more preferably be 80 DEG C at the most, be even more preferably 60 DEG C at the most.
The ordinary method of preparing powder paint compositions is: the component that each is weighed up is mixed in premixed device; the pre-composition that heating obtains is (for example, in kneader; preferably in forcing machine) thus extrudate obtained; cooling gained extrudate until its solidify; then be crushed into small-particle or thin slice; further grind and reduce particle size again, subsequently by suitable classification, thereby obtain the powder paint compositions that particle size is suitable.Therefore, the invention still further relates to the method for preparation powder paint compositions of the present invention, it comprises the following steps:
A. make each component of powder paint compositions mix to obtain pre-composition;
B. the pre-composition that obtains of heating, preferably in forcing machine, thereby obtains extrudate;
C. cooling gained extrudate, thereby the extrudate that obtains solidifying; And
D. the extrudate that solidifies obtaining is broken into less particle, thereby obtains powder paint compositions;
And preferably further comprise by sieve the step that prepared powder particle is classified, collection cut size is less than the sieve fraction of 90 μ m.
Optional conventional additive, for example filler/pigment, degasifier, flow agent or (light) stablizer of comprising of powder paint compositions of the present invention.The example of flow agent comprises Byk 361N.The example of suitable filler/pigment comprises metal oxide, silicate, carbonate or vitriol.The example of suitable stablizer comprises UV stablizer, for example phosphinate, thioether or HALS (hindered amine light stabilizer).The example of degasifier comprises bitter almond oil camphor and cyclohexane dimethanol bisbenzoate.Also can add other additives (for example improving the electrical additive of friction belt).
On the other hand, the present invention relates to a kind of method of coated substrate, it comprises the following steps:
1) powder paint compositions that comprises unsaturated polyester according to the present invention is coated on base material, thereby with the part or all of coated substrate of coating;
2) by obtained base material heating for some time being partly or entirely coated with, and heating time and temperature to make coating at least partly solidify.
Powder paint compositions of the present invention can apply by technology known to persons of ordinary skill in the art, for example, use electrostatic spraying or electrostatic fluidized bed.
In one of the present invention preferred embodiment, method of the present invention also comprises the step of diluting the unsaturated polyester resin that contains itaconic ester unit with one or more of reactive diluents, thereby obtains being applicable to build the resin combination of object.One preferred embodiment, the unsaturated polyester that contains itaconic ester is diluted in vinylbenzene, dimethyl itaconate and/or methacrylic ester.
According to the content of reactive diluent in this resin combination of the present invention conventionally in the scope of 5-75wt.%, preferably in the scope of 20-60wt.%, most preferably in the scope of 30-50wt.% (unsaturated polyester existing in respect to resin combination and the total amount of reactive diluent).Thinner can be for for example reducing the viscosity of resin combination, thereby make its processing simpler.For the sake of clarity, reactive diluent be can with the thinner of unsaturated polyester copolymerization.Ethylenically unsaturated compounds can be advantageously used for reactive diluent.Preferably, be used as thinner containing the compound of vinylbenzene, dimethyl itaconate and/or methacrylic ester.In an embodiment of the invention, be used as reactive diluent containing compound, NVP and/or the N-caprolactam of vinylbenzene, alpha-methyl styrene, 4-vinyl toluene, (methyl) acrylate.In this embodiment, preferably, be used as reactive diluent containing the compound of vinylbenzene and/or (methyl) acrylate, more preferably, be used as reactive diluent containing the compound of (methyl) acrylate.In another embodiment, methylene-succinic acid or itaconic ester are used as reactive diluent.In a preferred embodiment, reactive diluent comprises itaconic ester and at least one other ethylenically unsaturated compounds, for example vinylbenzene, alpha-methyl styrene, 4-vinyl toluene, (methyl) acrylate, NVP and/or N-caprolactam.In this embodiment, preferably, resin combination comprise itaconic ester as reactive diluent and vinylbenzene as reactive diluent or containing the compound of methacrylic ester as reactive diluent.Preferred itaconic ester is dimethyl itaconate.
Preferably, for the radically curing of resin combination, resin combination also comprises coinitiator, and its content arrives in the scope of 10wt% (with respect to the total amount of unsaturated polyester and reactive diluent) 0.00001.Preferred coinitiator is amine or transistion metal compound.
Preferably, the amine coinitiator may reside in composition is aromatic amine, is even more preferably fragrant tertiary amine.Suitable accelerator comprises DMA, N, N-Diethyl Aniline; Tolylamine and xylidine, for example N, N-diisopropanol-para-totuidine; N, N-dimethyl-para-totuidine; N, two (2-hydroxyethyl) xylidine and the N of N-, two (2-the hydroxyethyl)-Tolylamine of N-.The content of amine in resin combination (with respect to the total amount of unsaturated polyester and reactive diluent) is generally at least 0.00001wt.%, is preferably at least 0.01wt.%, is more preferably 0.1wt.% at least.Conventionally, in resin combination, the content of amine is 10wt.% at the most, is preferably 5wt.% at the most.
As the example of the suitable transistion metal compound of coinitiator be ordination number within the scope of 22-29 or ordination number for example, within the scope of 38-49 or the compound of the transition metal of ordination number within the scope of 57-79, the compound of vanadium, iron, manganese, copper, nickel, molybdenum, tungsten, cobalt, chromium.Preferred transition metal is V, Cu, Co, Mn and Fe.
Unsaturated polyester of the present invention can add extra free radical inhibitors after being diluted by reactive diluent.These free radical inhibitors are preferably selected from the group being made up of phenolic compound, benzoquinones, quinhydrones, catechol, stabilized radical and/or thiodiphenylamine.The amount of addible free radical inhibitors can change in quite wide scope, and can be selected as the primary index that reaches desired gel time.
In resin combination of the present invention, the example of operable suitable free radical inhibitors is for example: 2-methoxyphenol, 4-methoxyphenol, BHT, 2,6-, bis--tert.-butyl phenol, 2，4，6-trimethyl phenol, 2,4,6-, tri--dimethylaminomethylphenol, 4,4 '-sulfo--bis-(3 methy 6 tert butyl phenol), 4,4 '-isopropylidene biphenol, 2,4-, bis--tert.-butyl phenol, 6,6-, bis--tertiary butyl-2,2 '-methylene radical-bis--p-Cresol, quinhydrones, 2-toluhydroquinone, TBHQ, 2,5-, bis--tertiary butylated hydroquinone, 2,6-, bis--tertiary butylated hydroquinone, 2,6-dimethyl hydroquinone, TMHQ, catechol, 4-tert-butyl catechol, 4,6-, bis--tert-butyl catechol, benzoquinones, 2,3,5,6-tetrachloro-Isosorbide-5-Nitrae-benzoquinones, methylbenzoquinone, 2,6-phlorone, naphthoquinones, 1-oxygen base-2,2,6,6-tetramethyl piperidine, 1-oxygen base-2,2,6,6-tetramethyl piperidine-4-alcohol (being also referred to as the compound of TEMPOL), 1-oxygen base-2,2,6,6-tetramethyl piperidine-4-ketone (being also referred to as the compound of TEMPON), 1-oxygen base-2,2,6,6-tetramethyl--4-carboxyl-piperidines (being also referred to as the compound of 4-carboxyl-TEMPO), 1-oxygen base-2,2,5,5-tetramethyl--tetramethyleneimine, 1-oxygen base-2,2,5,5-tetramethyl--3-carboxy pyrrole alkane (also referred to as 3-carboxyl-PROXYL), jar (unit of capacitance) ten thousand oxyradicals (galvinoxyl), aluminium-N-nitroso-group phenyl azanol, diethyl hydroxylamine, the derivative of thiodiphenylamine and/or arbitrarily these compounds or combination.
Advantageously, in resin combination of the present invention the amount of free radical inhibitors (with respect to the total amount of unsaturated polyester and reactive diluent) in the scope of 0.0001-10 % by weight.More preferably, in resin combination the amount of free radical inhibitors in the scope of 0.001-1 % by weight.According to the type of selected inhibitor, those of ordinary skill in the art can quite easily estimate to cause the consumption according to good result of the present invention.
The invention still further relates to the radical-cured method of resin combination of the present invention that makes, be wherein cured by add above-mentioned initiator to resin combination.Preferably, in the temperature range of-20 to+200 DEG C, be cured, preferably in the temperature range of-20 to+100 DEG C, most preferably in the temperature range of-10 to+60 DEG C (so-called cold-curing).Initiator is light trigger, thermal initiator and/or redox initiator.
Light trigger represents to cause curing initiator by irradiation in this article.Light-initiated solidifying of being understood to that the irradiation (photoirradiation) of light by using suitable wavelength carries out.This is also referred to as photocuring.
Light initiation system can be made up of light trigger itself, or can be the combination of light trigger and sensitizing agent, or can be the mixture (alternatively with one or more of sensitizing agent combinations) of light trigger.
Available light initiation system in the context of the present invention can be selected from the group of light initiation system known to persons of ordinary skill in the art.For example, at " the Chemistry and Technology of UV and EB Formulations " of K.Dietliker and J.V.Crivello, the 3rd volume, 2
ndedition, (SITA Technology, London; 1998) in, can find a large amount of suitable light initiation systems.
Thermal initiator can be selected from azo-compound (for example Diisopropyl azodicarboxylate (AIBN)), C-C unstable compound (for example benzpinacone), superoxide and composition thereof.Preferably, thermal initiator is the combination of a kind of organo-peroxide or two or more organo-peroxides.
Preferably, redox initiator is the combination of organo-peroxide and at least one above-mentioned coinitiator.The example of suitable superoxide is such as hydroperoxide, peroxy carbonates (formula-OC (O) OO-), peroxy esters (formula-C (O) OO-), diacyl peroxide (formula-C (O) OOC (O)-), dialkyl peroxide (formula-OO-) etc.
The invention still further relates to goods and the parts made by unsaturated polyester resin, or relate to by make above-mentioned unsaturated polyester resin compositions solidify goods or the structure unit prepared with above-mentioned initiator.While use in this article, structural resin composition can provide structure unit.Common this resin combination is anhydrous system.Their common water (being mainly to obtain the reaction during resin is standby) that contains at the most 5 % by weight.While use in this article, it is 0.5mm and have suitable mechanical property at least that structure unit is regarded as thickness.The final application of resin combination of the present invention can be for example trolley part, ship, chemical anchor, roof, building, container, rebush (relining), pipe, bucket, floor, fan blade of windmill.
The present invention be more particularly directed to make resin combination of the present invention solidify the cured article or the structure unit that obtain by initiator (preferably comprising superoxide).According to an embodiment, preferably, be cured by molding, thereby be more preferably cured and obtain especially SMC or BMC parts by compression molding.Preferably, at the temperature of at least 130 DEG C, carry out molding, more preferably at the temperature of at least 140 DEG C, carry out molding; At the temperature of 170 DEG C at the most, more preferably carrying out molding at the temperature of 160 DEG C at the most.
Now by a series of embodiment and comparative example explanation the present invention.All embodiment support the scope of claim.But the present invention is not limited to the specific implementations shown in embodiment.
the resin of standard is synthetic
Glycol, diacid and/or acid anhydrides, optional inhibitor and catalyzer are added in the reactor that is equipped with packed column, temperature measuring equipment and inert gas entrance.Make mixture slowly be heated to 200 DEG C by ordinary method.Make mixture in reactor keep 200 DEG C until the distillation of water stop.Remove packed column, mixture is kept under low pressure until acid number reaches the numerical value lower than 50mg KOH/ (g resin).Then, remove and put vacuum by rare gas element, mixture is cooled to 130 DEG C or lower.Obtain by this method solid UP resin.Then solid resin is dissolved in to temperature lower than in the reactive diluent of 80 DEG C.
curing monitoring
Solidify by the monitoring of standard gel time device.This represents, in the time of peroxide cure shown in resin use, to determine gel time (T according to DIN 16945 methods by heat release measurement
gelor T
25-> 35 dEG C) and peak time (T
peakor T
25-> peak).
the mensuration of mechanical property
Prepare the casting material of watering of 4mm in order to measure mechanical property.After 16 hours, water casting material and take out from mould, after fixing 24 hours at 60 DEG C, then after fixing 24 hours at 80 DEG C.
Measure the mechanical property of cured article according to ISO 527-2.Measure heat-drawn wire (HDT) according to ISO 75-A.
Use Physica instrument at 23 DEG C, to measure the viscosity of the resin dissolving.Use cone/panel assembly (Brookfield CAP200+cone 3) at 125 DEG C, to measure the viscosity of virgin resin.
comparative experiment A-K and embodiment 1-2
Prepare resin by standard building-up process by the listed component of table 1 and inhibitor.
Clearly prove following truth in conjunction with Comparative experiment A and B and embodiment 1 and 2: content can be successfully for the preparation of methylene-succinic acid resin higher than benzoquinones and the alkylating benzoquinones of 100ppm, wherein uses content will cause gel lower than 100ppm or lower benzoquinones and alkylating benzoquinones.This is surprising to consider following truth: low and other inhibitor (comparative example G-J) high-content all cause other inhibitor (comparative example E-F) of gel or low or high-content all to cause the liquid resin at 125 DEG C.In addition, by embodiment 1 and 2 and the comparison of contrast experiment F, show that obtained resin has similar viscosity, the benzoquinones that therefore benzoquinones and alkyl replace is the good surrogate of quinhydrones.
embodiment 3-7 and contrast experiment L
Prepare resin by standard building-up process by the listed component of table 2 and inhibitor.Use 0.5wt% cobalt liquor (NL-49P), carry out cured resin with the Trigonox 44B of 2wt% as superoxide subsequently.Monitor curing by gel time equipment.
table 2
| Embodiment 3 | L | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Methylene-succinic acid | 732 | 732 | 732 | 732 | 732 | 732 |
| Propylene glycol | 471 | 471 | 471 | 471 | 471 | |
| 1,3-PD | 235.5 | |||||
| Ethylene glycol | 192.1 | |||||
| Benzoquinones | 0.6 | 0.3 | 0.3 | |||
| 2-methylbenzoquinone | 0.6 | 0.3 | 0.3 | 0.3 | ||
| Quinhydrones | 0.6 | |||||
| 2-toluhydroquinone | 0.3 | |||||
| Viscosity (cone/plate) dPa.s 125 DEG C time | 4.65 | 4.25 | 4.05 | 3.48 | 3.36 | 2.60 |
| The acid number (mgKOH/g resin) of resin | 45 | 44 | 45 | 45 | 45 | 45 |
| Reactive diluent | Vinylbenzene | Vinylbenzene | Vinylbenzene | Vinylbenzene | Vinylbenzene | Vinylbenzene |
| Solid content % | 65 | 65 | 65 | 65 | 65 | 65 |
| Viscosity mPa.s 23 DEG C time | 976 | 816 | 770 | 655 | 630 | 423 |
| Tensile strength (MPa) | 71 | 58 | 63 | 56 | 57 | 43 |
| Tensile modulus (GPa) | 3.6 | 2.6 | 3.5 | 3.4 | 3.6 | 3.1 |
| Elongation at break (%) | 2.4 | 4.3 | 2.2 | 1.9 | 1.8 | 1.4 |
| Flexural strength (MPa) | 105 | 87 | 116 | 120 | 127 | 102 |
| Modulus in flexure (GPa) | 3.9 | 2.8 | 3.8 | 3.5 | 3.7 | 3.3 |
| Barcol hardness | 42 | 35 | 43 | 45 | 47 | 42 |
| HDT(℃) | 98 | 85 | 98 | 98 | 101 | 103 |
From this table, be clear that: the inhibitor of the application of the invention has improved the mechanical property of cured resin.By embodiment 3 or 4 and the comparison of contrast experiment L, clearly illustrate that the impact on tensile strength, tensile modulus, flexural strength, modulus in flexure, Barcol hardness, particularly on the impact by the represented thermostability of HDT.
This is surprising, because table 1 shows: compared with quinhydrones, the benzoquinones that benzoquinones and alkyl replace is the inhibitor that efficiency is lower, in the time using the benzoquinones of 100ppm or the benzoquinones of alkyl replacement, resin will produce gel (Comparative experiment A and B).
Embodiment 5 illustrates: can use the mixture of the benzoquinones of benzoquinones and alkyl replacement, and this combination is by the synergistic effect producing resin viscosity, has kept thermostability simultaneously.Embodiment 6 illustrates: can use the benzoquinones of alkyl replacement and the mixture of quinhydrones, thereby can realize the increase of flexural strength compared with embodiment 4.Embodiment 7 explanations can be used different glycol.
Claims (20)
1. one kind for the preparation of comprising the method for itaconic ester unit as the unsaturated polyester resin of reactive unsaturated group, wherein said method comprises under the existence that at least makes the benzoquinones that methylene-succinic acid and/or itaconic anhydride and at least one glycol replace at benzoquinones and/or alkyl reacts, and the total amount of the benzoquinones that wherein benzoquinones and alkyl replace is 200ppm at least.
2. the method for claim 1, the total amount of the benzoquinones that wherein benzoquinones and alkyl replace is 300ppm at least.
3. the method for claim 1, the total amount of the benzoquinones that wherein benzoquinones and alkyl replace is 400ppm at least.
4. the method for claim 1, carries out under the existence of the benzoquinones that wherein said method replaces at alkyl.
5. the method for claim 1, carries out under the benzoquinones that wherein said method replaces at alkyl and the existence of benzoquinones.
6. method as claimed in claim 5, carries out under the existence of the benzoquinones that wherein said method replaces at 200ppm alkyl at least and at least 200ppm benzoquinones.
7. the method as described in any one in claim 1-6, the benzoquinones that wherein said alkyl replaces is 2-methylbenzoquinone.
8. the method as described in any one in claim 1-6, wherein said method also comprises the step by reactive diluent letdown resin.
9. method as claimed in claim 8, wherein said resin is diluted in vinylbenzene, dimethyl itaconate and/or methacrylic ester.
10. method as claimed in claim 8, the benzoquinones that wherein said alkyl replaces is 2-methylbenzoquinone.
11. methods as claimed in claim 10, wherein said resin is diluted in vinylbenzene, dimethyl itaconate and/or methacrylic ester.
12. 1 kinds of resin combinations, it comprises: the benzoquinones that the unsaturated polyester resin that contains itaconic ester unit and benzoquinones and/or alkyl replace.
13. resin combinations as claimed in claim 12, wherein said resin combination comprises the benzoquinones that benzoquinones and/or alkyl replace, and the total amount of the benzoquinones that wherein benzoquinones and alkyl replace is 200ppm at least.
14. resin combinations described in claim 12 or 13, the benzoquinones that wherein said alkyl replaces is 2-methylbenzoquinone.
15. resin combinations as described in any one in claim 12-14, wherein said composition also comprises reactive diluent.
16. use initiators solidify the resin combination described in any one in claim 12-15 and the cured article or the structure unit that obtain.
17. cured article as claimed in claim 16 or structure units, wherein said initiator comprises superoxide.
Cured article described in 18. claims 16 or 17 or the structure unit purposes in trolley part, ship, chemical anchor, roof, building, container, rebush, pipe, floor or fan blade of windmill.
Cured article described in 19. claims 16 or 17 or the structure unit purposes in bucket
20. powder paint compositions that comprise the unsaturated polyester resin compositions described in any one in claim 12-15.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09156139.9 | 2009-03-25 | ||
| EP09156131.6 | 2009-03-25 | ||
| EP09156130 | 2009-03-25 | ||
| EP09156137 | 2009-03-25 | ||
| EP09156131 | 2009-03-25 | ||
| EP09156137.3 | 2009-03-25 | ||
| EP09156142.3 | 2009-03-25 | ||
| EP09156139 | 2009-03-25 | ||
| EP09156130.8 | 2009-03-25 | ||
| EP09156142 | 2009-03-25 | ||
| PCT/EP2010/053853 WO2010108968A1 (en) | 2009-03-25 | 2010-03-24 | Process for preparing unsaturated polyester |
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| Publication Number | Publication Date |
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| CN102361908A CN102361908A (en) | 2012-02-22 |
| CN102361908B true CN102361908B (en) | 2014-07-09 |
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| CN201080013565.3A Active CN102361906B (en) | 2009-03-25 | 2010-03-24 | Unsaturated polyester |
| CN2010800135649A Active CN102361905B (en) | 2009-03-25 | 2010-03-24 | Unsaturated polyester resin |
| CN201080013577.6A Active CN102361907B (en) | 2009-03-25 | 2010-03-24 | Unsaturated polyester resin composition |
| CN201080013579.5A Active CN102361908B (en) | 2009-03-25 | 2010-03-24 | Process for preparing unsaturated polyester |
| CN2010800136389A Active CN102361909B (en) | 2009-03-25 | 2010-03-24 | Process for preparing unsaturated polyester |
| CN201080013561.5A Active CN102361904B (en) | 2009-03-25 | 2010-03-24 | Unsaturated polyester resin |
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| CN201080013565.3A Active CN102361906B (en) | 2009-03-25 | 2010-03-24 | Unsaturated polyester |
| CN2010800135649A Active CN102361905B (en) | 2009-03-25 | 2010-03-24 | Unsaturated polyester resin |
| CN201080013577.6A Active CN102361907B (en) | 2009-03-25 | 2010-03-24 | Unsaturated polyester resin composition |
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| CN201080013561.5A Active CN102361904B (en) | 2009-03-25 | 2010-03-24 | Unsaturated polyester resin |
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| US (6) | US20120101226A1 (en) |
| EP (6) | EP2411443B2 (en) |
| JP (6) | JP2012521471A (en) |
| CN (6) | CN102361906B (en) |
| BR (6) | BRPI1009835A2 (en) |
| DK (3) | DK2411445T4 (en) |
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| WO (6) | WO2010108966A1 (en) |
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